WO2020178892A1 - Agent conférant une capacité de prévention de l'encrassement et membrane de traitement de l'eau fabriquée à l'aide de celui-ci - Google Patents

Agent conférant une capacité de prévention de l'encrassement et membrane de traitement de l'eau fabriquée à l'aide de celui-ci Download PDF

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WO2020178892A1
WO2020178892A1 PCT/JP2019/008069 JP2019008069W WO2020178892A1 WO 2020178892 A1 WO2020178892 A1 WO 2020178892A1 JP 2019008069 W JP2019008069 W JP 2019008069W WO 2020178892 A1 WO2020178892 A1 WO 2020178892A1
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Prior art keywords
water treatment
membrane
fouling
imparting agent
ability
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PCT/JP2019/008069
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English (en)
Japanese (ja)
Inventor
後藤　淳
蓉 王
苗 田
泰之 三好
大昂 溝口
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ナンヤン テクノロジカル ユニヴァーシティー
株式会社日本触媒
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Application filed by ナンヤン テクノロジカル ユニヴァーシティー, 株式会社日本触媒 filed Critical ナンヤン テクノロジカル ユニヴァーシティー
Priority to US17/435,289 priority Critical patent/US11919986B2/en
Priority to PCT/JP2019/008069 priority patent/WO2020178892A1/fr
Priority to CN201980093283.XA priority patent/CN113490540B/zh
Priority to JP2021503248A priority patent/JP7256505B2/ja
Publication of WO2020178892A1 publication Critical patent/WO2020178892A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/281—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by applying a special coating to the membrane or to any module element
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/03—Pressure
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present invention relates to a fouling suppression ability-imparting agent and a water treatment membrane using the same.
  • Water treatment membranes are membranes used to treat water containing impurities, and their use is expanding as wastewater standards and water quality standards are strengthened in various countries around the world. Applications in which water treatment membranes are used include water purification treatment, process water production, sewage treatment, industrial wastewater treatment, desalination of seawater, etc., precision filtration membranes, ultrafiltration membranes, nanofiltration membranes, reverse osmosis membranes, etc. Various water treatment membranes such as a forward osmosis membrane and an ion exchange membrane are used properly according to the application.
  • a surface treatment agent for a polyamide reverse osmosis membrane containing (see Patent Document 1) and a method of making the reverse osmosis membrane hydrophilic by contacting a modified polyvinyl alcohol having a polyalkylene oxide chain (see Patent Document 2).
  • Patent Document 1 a modified polyvinyl alcohol having a polyalkylene oxide chain
  • Patent Document 2 a modified polyvinyl alcohol having a polyalkylene oxide chain
  • Patent Document 3 a method of subjecting a reverse osmosis membrane to a betaine compound having a polyalkylene oxide chain to perform a stain resistance treatment of the reverse osmosis membrane
  • a porous composition composed of a copolymer having a constituent unit [A] of the above and a monomer unit [B] having a predetermined structure having a butyl group at the end of the side chain in a predetermined ratio and having a predetermined weight average molecular weight.
  • a fouling inhibitor for a filtration membrane (see Patent Document 4) is disclosed.
  • a technique has been proposed in which a hydrophilic resin is brought into contact with a water treatment membrane to carry out a hydrophilic treatment for suppressing fouling, and various hydrophilic resins for that purpose have been proposed.
  • RO membrane reverse osmosis membrane
  • the conventional hydrophilic resin does not have sufficient adhesion to the membrane, and the RO membrane becomes hydrophilic when used for a long period of time. The resin loses its ability to suppress fouling.
  • the conventional hydrophilic resin has sufficient adhesiveness to a wide range of water treatment membranes and cannot impart excellent fouling suppressing ability.
  • the present invention has been made in view of the above situation, and has good adhesion to various water treatment membranes such as RO membrane, and fouling suppression ability capable of imparting excellent fouling suppression ability.
  • the purpose is to provide an imparting agent.
  • the present inventor has investigated a fouling-suppressing ability-imparting agent that has good adhesion to various water treatment membranes such as RO membranes and can impart excellent fouling-suppressing ability, and has an oxy group on the side chain.
  • a structural unit (I) having a specific structure having an alkylene group and a hydroxyl group-containing alkyl group at the side chain terminal, and an oxyalkylene group at the side chain, and a specific side chain terminal having a hydrogen atom or an alkyl group
  • the present invention has been found out that a copolymer having a structural unit (II) with a structure has good adhesion to various water treatment membranes and can impart excellent fouling suppression ability, and has reached the present invention. Is.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a direct bond, —CH 2 —, —CH 2 CH 2 —, or —CO—.
  • R 3 is the same or different.
  • X represents —CH 2 CH(OH)CH 2 (OH), or —CH(—CH 2 OH) 2
  • n is an addition mole of an oxyalkylene group.
  • R 4 represents a hydrogen atom or a methyl group.
  • R 5 represents a direct bond, —CH 2 —, —CH 2 CH 2 —, or —CO—.
  • R 6 is the same or different.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • M is the number of added moles of the oxyalkylene group and represents a number of 1 to 100.
  • the copolymer preferably has a weight average molecular weight of 1,000 to 1,000,000.
  • the present invention is also a water treatment membrane characterized by being treated with the fouling suppressing ability-imparting agent of the present invention.
  • the agent for imparting fouling suppression ability of the present invention has good adhesion to various water treatment membranes such as microfiltration membrane, ultrafiltration membrane, nanofiltration membrane, reverse osmosis membrane, forward osmosis membrane and ion exchange membrane. It is possible to give excellent fouling suppression ability, and the flux recovery rate by washing is high even after the foulant is attached. Therefore, by using the fouling-suppressing ability-imparting agent of the present invention, the water treatment membrane can exhibit an excellent fouling-suppressing ability for a long period of time.
  • the fouling inhibitory ability imparting agent of the present invention comprises a structural unit (I) represented by the above general formula (1) and a structural unit (II) represented by the above formula (2). It is characterized by including a copolymer having.
  • the copolymer contained in the fouling suppressing ability-imparting agent of the present invention may have one type of structural unit corresponding to the structural unit (I) and one type of structural unit corresponding to the structural unit (II), respectively. You may have more than one. As long as it has the structural units (I) and (II), it may have one or more other structural units other than the structural units.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 is a direct bond, -CH 2 -, - CH 2 CH 2 -, or -CO- represents an, in terms of affinity for water treatment membrane is preferably -CO-.
  • R 3 s are the same or different and each represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group preferably has 1 to 10 carbon atoms from the viewpoint of affinity for the water treatment membrane. It is more preferably 1 to 5, and even more preferably 2 to 3.
  • n is the number of moles added to the oxyalkylene group and represents a number of 0 to 100, but is preferably a number of 0 to 50 from the viewpoint of affinity for the water treatment membrane. The number is more preferably 0 to 20, and further preferably 0 to 5.
  • R 4 represents a hydrogen atom or a methyl group.
  • R 5 represents a direct bond, —CH 2 —, —CH 2 CH 2 —, or —CO—.
  • R 6 s are the same or different and each represents an alkylene group having 1 to 20 carbon atoms, but the alkylene group preferably has 1 to 10 carbon atoms from the viewpoint of affinity for the water treatment membrane. It is more preferably 1 to 5, and even more preferably 2 to 3.
  • R 7 represents a hydrogen atom or an alkylene group having 1 to 20 carbon atoms, and is preferably a hydrogen atom or an alkylene group having 1 to 15 carbon atoms from the viewpoint of affinity for the water treatment membrane.
  • a hydrogen atom or an alkylene group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or an alkylene group having 1 to 5 carbon atoms is more preferable.
  • m is the number of moles added to the oxyalkylene group and represents a number of 1 to 100, but it is preferably a number of 1 to 80 from the viewpoint of affinity for the water treatment membrane. The number is more preferably 1 to 60, further preferably 3 to 55.
  • the proportion of the structural unit (I) represented by the general formula (1) is preferably 5 to 99 mol% based on 100 mol% of all structural units. It is more preferably 10 to 99 mol %, and even more preferably 20 to 99 mol %.
  • the proportion of the structural unit (II) represented by the general formula (2) is preferably 1 to 95 mol% based on 100 mol% of all structural units. It is more preferably 1 to 90 mol %, and even more preferably 1 to 80 mol %.
  • the monomer forming the structural unit (I) and the monomer forming the structural unit (II) are preferably monomers represented by the following general formulas (3) and (4), respectively.
  • Examples of the monomer represented by the general formula (3) include glycerol mono(meth)acrylate.
  • Examples of the monomer represented by the general formula (4) include ethoxy-diethylene glycol (meth) acrylate, methoxy-triethylene glycol (meth) acrylate, 2-ethylhexyl-diethylene glycol (meth) acrylate, and methoxy-polyethylene glycol (meth). ) Alkoxyalkylene glycol (meth) acrylates such as acrylate, methoxy-dipropylene glycol (meth) acrylate, phenoxy-diethylene glycol (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate, and alkylene oxide adducts of (meth) allyl alcohol.
  • alkoxyalkylene glycol having an (iso)propenyl group such as an alkylene oxide adduct of isoprenol.
  • methoxy-polyethylene glycol (meth)acrylate and isoprenol alkylene oxide adducts are preferable from the viewpoint of hydrophilicity.
  • the monomer forming the other structural units is an ethylenic unsaturated group having a cationic group such as amine.
  • the proportion of the other structural units other than the structural units (I) and (II) in the copolymer is preferably 80 mol% or less based on 100 mol% of all structural units. It is more preferably 60 mol% or less, and further preferably 40 mol% or less.
  • the copolymer preferably has a weight average molecular weight of 1,000 to 1,000,000. With such a molecular weight, it becomes possible to achieve both the adhesion to the film and the fouling suppression ability. It is more preferably 5,000 to 500,000, and even more preferably 10,000 to 200,000.
  • the weight average molecular weight of the copolymer can be measured by gel permeation chromatography (GPC) by the method described in Examples below.
  • the method for producing the copolymer is a monomer represented by the general formula (3), a monomer represented by the general formula (4), and other monomers used as necessary.
  • a monomer represented by the general formula (3) There is no particular limitation so long as the above copolymer is produced from the above, and any polymerization reaction of radical polymerization, cationic polymerization, and anionic polymerization may be used.
  • the polymerization reaction may be either photopolymerization or thermal polymerization.
  • the polymerization reaction at the time of producing the copolymer is preferably carried out using a polymerization initiator, and the polymerization initiator may be a radical polymerization initiator, a cationic polymerization initiator, or an anionic polymerization initiator, depending on the type of polymerization reaction. Can be used accordingly. As these polymerization initiators, those usually used can be used. The amount of the polymerization initiator used is preferably 0.001 to 1 mol based on 1 mol of the total monomers used for the polymerization reaction.
  • the fouling suppressing ability-imparting agent of the present invention may contain other components as long as it contains the above-mentioned copolymer.
  • other components include one or more of pH stabilizers such as phosphates, antibacterial components such as sodium hypochlorite; lower alcohols such as methanol, ethanol and propanol.
  • the content of the other components in the fouling inhibitory ability-imparting agent of the present invention is not particularly limited as long as it does not inhibit the fouling inhibitory ability, but is based on 100% by mass of the copolymer contained in the fouling inhibitory ability imparting agent. Therefore, it is preferably 40% by mass or less. More preferably, it is 20 mass% or less.
  • the fouling suppression ability-imparting agent of the present invention may be used in the form of an aqueous solution.
  • the concentration of the copolymer in the aqueous solution is not particularly limited, but is preferably 0.1 to 50,000 mg/L. With such a concentration, the aqueous solution has a viscosity that is easy to handle, and the treatment time for imparting the fouling suppressing ability to the water treatment membrane does not become too long and inefficient.
  • the concentration of the aqueous solution is more preferably 0.1 to 20,000 mg/L, further preferably 0.1 to 10,000 mg/L.
  • the water used when preparing the aqueous solution of the fouling suppression ability-imparting agent is not particularly limited, but water with a low ion load such as demineralized water is preferable. Further, a fouling suppressing ability-imparting agent may be added to water to be treated with the water treatment membrane to prepare an aqueous solution and the water treatment membrane may be treated with the aqueous solution.
  • the method for imparting fouling suppressing ability to a water treatment membrane using the fouling inhibiting ability imparting agent of the present invention is not particularly limited, and the present invention can be used as a raw material of the membrane before forming the water treatment membrane. After mixing the fouling suppression ability-imparting agent, a method for forming a water treatment film using the raw material, or a copolymer contained in the fouling suppression ability-imparting agent of the present invention on the raw material resin surface of the water treatment membrane.
  • Examples include a method of bonding by graft polymerization, a method of coating the surface of the water treatment membrane with the fouling-suppressing ability-imparting agent of the present invention, a method of contacting an aqueous solution of the fouling-suppression-ability imparting agent of the present invention with the water treatment membrane. ..
  • the aqueous solution of the fouling suppression ability imparting agent of the present invention is contacted with the water treatment film to impart the fouling suppression ability to the water treatment film.
  • the method is preferred. By using this method, it is possible to impart the fouling suppressing ability to the water treatment membrane at the same time while performing the water treatment by the water treatment apparatus, and the most easily imparting the fouling inhibiting ability to the water treatment membrane. ..
  • the method of contacting the aqueous solution of the fouling inhibitory ability-imparting agent of the present invention with the water treatment membrane is not particularly limited as long as the fouling inhibitory ability is imparted by the method, but the aqueous solution of the fouling inhibitory ability imparting agent is watered.
  • a method in which pressurized water is passed through the treated membrane is preferable.
  • an aqueous solution of the fouling suppression ability-imparting agent may be passed under pressure through a water treatment membrane installed separately from the water treatment device.
  • the fouling inhibition ability imparting agent of the present invention is added to the water to be treated during the operation of the water treatment device.
  • the treatment and the fouling suppression ability imparting treatment may be carried out simultaneously, or only the fouling suppressing ability imparting treatment may be carried out without water treatment.
  • the pressure at which the aqueous solution of the fouling suppressing ability-imparting agent is pressurized and passed through the water treatment membrane is not particularly limited as long as the fouling suppressing ability is imparted, but is 0.1 to 12 MPa. It is preferable. Further, the flux for passing water is not particularly limited, but is preferably about 0.1 to 15 m 3 /m 2 /day. By carrying out under such water flow conditions, it is possible to sufficiently impart the fouling suppressing ability while preventing the decrease of the flux from becoming too large.
  • the time for treating the water treatment membrane by passing an aqueous solution of the fouling suppressing ability-imparting agent under pressure is not particularly limited, but while preventing the decrease of the flux from becoming too large, the fouling suppressing ability is sufficiently increased. Considering application, it is preferably 1 to 1,000 hours. More preferably, it is 2 to 300 hours.
  • the treatment temperature when the aqueous solution of the fouling suppressing ability-imparting agent is pressurized and passed through the water treatment film is not particularly limited, but the decrease in the flux is prevented from becoming too large, and Considering suppression of denaturation, 5 to 60°C is preferable. More preferably, it is 10 to 50°C.
  • Fouling suppressing method The fouling suppressing ability-imparting agent of the present invention can impart the fouling suppressing ability to a water treatment film, but even if the fouling-suppressing ability imparting agent of the present invention is used, water is retained for a long period of time. When used for treatment, it is unavoidable that the foulant gradually adheres to the water treatment membrane and the water permeability decreases. However, the permeability of the water treatment membrane can be restored by removing the foulant attached to the membrane.
  • the method for removing the foulant adhering to the membrane is not particularly limited, but the foulant can be effectively removed by mechanical peeling washing and / or chemical washing, and the transmittance of the water-treated membrane can be restored.
  • the water treatment membrane treated with the agent for imparting fouling suppression ability of the present invention has a high flux recovery rate by such cleaning, by combining such cleaning, excellent fouling suppression ability over a long period of time is obtained. Can be demonstrated.
  • a method for suppressing fouling which also includes the step of removing the foulant and recovering the transmittance of the water treatment membrane, that is, the following general formula (1);
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a direct bond, —CH 2 —, —CH 2 CH 2 —, or —CO—.
  • R 3 is the same or different.
  • X represents —CH 2 CH(OH)CH 2 (OH), or —CH(—CH 2 OH) 2
  • n is an addition mole of an oxyalkylene group.
  • R 4 represents a hydrogen atom or a methyl group.
  • R 5 represents a direct bond, —CH 2 —, —CH 2 CH 2 —, or —CO—.
  • R 6 is the same or different.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • M is the number of added moles of the oxyalkylene group and represents a number of 1 to 100.
  • a method for suppressing fouling of a water-treated film which comprises a step of washing the water-treated film by mechanical peeling and / or chemical washing to remove foulants adhering to the water-treated film, is also one of the present inventions.
  • the step of removing the foulant is performed by mechanical peeling cleaning and/or chemical cleaning.
  • the chemical washing may be any method as long as it is a method for removing the foulant adhering to the water treatment membrane with a chemical agent, but it is not limited to acid and/or its salt (hereinafter referred to as acid (salt)) or alkali. It is preferable that the cleaning is performed using at least one kind of cleaning agent.
  • the mechanical peeling cleaning may be any method as long as it is a method of removing the foulant attached to the water treatment film by a mechanical peeling force, and is performed by cleaning using ultrasonic waves, bubbles, or backwashing. be able to.
  • Backwashing is a method in which water is applied to the water treatment film in a direction opposite to that during water treatment to remove the foulant adhering to the water treatment film by a mechanical peeling force.
  • the flux when water is passed through the water treatment membrane in the direction opposite to that for water treatment but sufficient removal of foulant and efficiency of the washing process should be considered.
  • it is preferably 0.1 to 15 m 3 /m 2 /day.
  • water may be passed under pressure, and there is no particular limitation on the pressure when the water is passed under pressure, but in consideration of sufficient removal of the foulant and no adverse effect on the membrane, It is preferably from 1 to 12 Mpa.
  • the acids include hydrochloric acid, sulfuric acid, nitrate, nitrite, carbonic acid, phosphoric acid and hypochlorite.
  • inorganic acids such as hypoiodic acid, formic acid, acetic acid, citric acid, propionic acid, butyric acid, oxalic acid, lactic acid, maleic acid, fumaric acid, succinic acid and benzoic acid
  • the acid salts may be, for example, alkali metal salts such as sodium salts and potassium salts, or organic salts such as ammonium salts.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and one or more species such as sodium dodecyl sulfate and tetrasodium ethylenediaminetetraacetate can be used.
  • the concentration of acid (salt) or alkali used for the above washing is not particularly limited, but considering that the foulant is sufficiently removed without adversely affecting the water treatment membrane, the ratio of solute to water is 0.1 to It is preferably 60% by mass.
  • the method of washing the water treatment membrane with the detergent is to wash the water treatment membrane.
  • the water treatment membrane is not particularly limited as long as it is, and may be washed by removing the water treatment membrane from the water treatment device and immersing it in the detergent, or by allowing the detergent to pass through the water treatment membrane. You may wash by passing a cleaning agent through the water treatment film
  • the fouling inhibitory ability imparting agent of the present invention has good adhesion to various water treatment membranes such as RO membranes and can impart excellent fouling inhibitory ability.
  • the water treatment membrane treated with the fouling suppressing ability-imparting agent of the present invention can exhibit an excellent fouling suppressing ability for a long period of time.
  • a water treatment membrane obtained by such treatment with the fouling suppressing ability-imparting agent of the present invention is also one aspect of the present invention.
  • Specific examples of the water treatment membrane include microfiltration membrane, ultrafiltration membrane, nanofiltration membrane, RO membrane, forward osmosis membrane, and ion exchange membrane.
  • the water treatment membrane of the present invention can be suitably used for various water treatment systems including an ultrapure water production system and a waste water recovery system.
  • AM-90G 2 mass% sodium persulfate aqueous solution (hereinafter referred to as 2% NaPS) 22.5 parts, 35 mass% sodium hydrogen sulfite aqueous solution (hereinafter referred to as 35% SBS) 0.9 parts and 20 parts of pure water were dropped from separate dropping nozzles.
  • the dropping time of each dropping solution was 180 minutes for GLMM, 180 minutes for AM-90G, 210 minutes for 2% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water.
  • the dropping was started at the same time, the dropping rate was kept constant, and the dropping was continued.
  • the reaction solution was kept at 80° C. for 30 minutes for aging to complete the polymerization.
  • a copolymer (1) having a weight average molecular weight of 54,000 was obtained.
  • Example 2 To a 50 mL screw tube, add 109.2 parts of pure water, 26.6 parts of GLMM, 2.9 parts of AM-90G, 0.09 parts of NaPS and 0.064 parts of SBS, and use an automatic synthesizer to make 80 After the temperature was raised to °C, stirring was carried out for 3 hours to complete the polymerization. Thus, a copolymer (2) having a weight average molecular weight of 120,000 was obtained.
  • Example 3 In Example 1, 34.8 parts of pure water, 19.2 parts of GLMM, 14.5 parts of AM-90G, 22.5 parts of 2% NaPS, 1.3 parts of 35% SBS, Polymerization was performed in the same manner as in Example 1 except that the amount of pure water dropped was changed to 20 parts to obtain a copolymer (3) having a weight average molecular weight of 19,000.
  • Example 4 1.5 parts of GLMM, 0.014 parts of ethyl ⁇ -iodophenylacetate, 0.003 parts of 2,2′-azobis(2,4-dimethylvaleronitrile), 0.043 parts of tetrabutylammonium iodide in a 30 mL Schlenk tube. And 2.25 parts of ethanol were added, the inner space of the Schlenk tube was replaced with argon gas. The reaction was carried out by stirring the contents of the Schlenk tube at 60° C. for 25 minutes. After the reaction was completed, the obtained reaction solution was added dropwise to diethyl ether to obtain a first stage polymer.
  • the polymer had a number average molecular weight Mn of 8,000 and a weight average molecular weight of 10,000.
  • the obtained polymer was 0.042 part, AM-90G 0.26 part, 4,4′-azobis(4-cyanovaleric acid) 0.002 part, and sodium iodide 0.003 part.
  • 4.29 parts of ion-exchanged water were added, and then the inner space of the eggplant flask was replaced with argon gas.
  • the reaction was carried out by stirring the contents of the eggplant flask at 90° C. for 3 hours.
  • the block copolymer (4) had a number average molecular weight Mn of 14,000 and a weight average molecular weight of 23,000.
  • the molar ratio of the glycerol monomethacrylate unit and the methoxypolyethylene glycol acrylate unit contained in the block copolymer (4) calculated from the number average molecular weight Mn of the polymer of the first stage and the block copolymer (4) is It was 78:22.
  • Example 5 In Example 2, 20.2 parts of pure water, GLMM of 4.38 parts glycerin monoacrylate (hereinafter referred to as GLMA), AM-90G of 3.62 parts, NaPS of 0.11 parts, and SBS of 0.07. Polymerization was performed in the same manner as in Example 2 except that parts were changed to obtain a copolymer (5) having a weight average molecular weight of 51,000.
  • GLMA glycerin monoacrylate
  • AM-90G 3.62 parts
  • NaPS sodiumPS of 0.11 parts
  • SBS SBS
  • Example 6 In Example 5, 15.0 parts of pure water, 5.85 parts of GLMA, AM-90G of 1.60 parts of a 60% aqueous solution of an isoprenol EO50 mol adduct (referred to as IPN-50), and NaPS of 0.12. Parts and SBS were changed to 0.06 parts to carry out polymerization in the same manner as in Example 5 to obtain a copolymer (6) having a weight average molecular weight of 48,000.
  • IPN-50 isoprenol EO50 mol adduct
  • Comparative Example 1 In Example 1, 48.5 parts of pure water, 57.9 parts of AM-90G, 18.0 parts of 2% NaPS, 0.3 parts of 35% SBS were dropped without using GLMM. Polymerization was performed in the same manner as in Example 1 except that the amount of pure water used was changed to 20 parts to obtain a comparative polymer (1) having a weight average molecular weight of 43,000.
  • Comparative example 2 Same as Example 1 except that AM-90G was not used and the amount of pure water initially charged was changed to 44.7 parts, GLMM to 32.0 parts, and 2% NaPS to 30.0 parts. Polymerization was performed to obtain a comparative polymer (2) having a weight average molecular weight of 47,000.
  • the UF membrane modified with the copolymer of the present invention has a high flux when an aqueous solution containing a foulant is passed, and also has a good flux recovery rate. It was confirmed that the copolymer of the present invention can impart excellent fouling suppressing ability to the water treatment membrane.
  • the dropping was started at the same time, the dropping rate was kept constant, and the dropping was continued. After the dropwise addition was completed, the reaction solution was kept at 80° C. for 30 minutes for aging to complete the polymerization. In this way, a copolymer (7) having a weight average molecular weight of 47,200 was obtained.
  • Example 8 Polymerization was performed in the same manner as in Example 7 except that 35% SBS was changed to 0.50 part in Example 7, to obtain a copolymer (8) having a weight average molecular weight of 54,200.
  • Example 9 Polymerization was performed in the same manner as in Example 3 except that 35% SBS was changed to 1.0 part to obtain a copolymer (9) having a weight average molecular weight of 23,700.

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Abstract

La présente invention concerne un agent conférant une capacité de prévention de l'encrassement qui présente une bonne adhérence à diverses membranes de traitement de l'eau comprenant une membrane d'osmose inverse et peut conférer une excellente capacité de prévention de l'encrassement. La présente invention concerne un agent conférant une capacité de prévention d'encrassement caractérisé en ce qu'il comprend un copolymère ayant une unité structurale (I) représentée par la formule générale (1) (dans laquelle R1 représente un atome d'hydrogène ou un groupe méthyle ; R2 représente une liaison directe,-CH2-, -CH2CH2- ou -CO- ; R3's peuvent être identiques ou différents les uns des autres et représentent indépendamment un groupe alkylène ayant 1 à 20 atomes de carbone ; X représente -CH2CH(OH)CH2(OH) ou -CH(-CH2OH)2 ; et n représente le nombre de moles de groupes oxyalkylène ajoutés et représente une valeur numérique de 0 à 100) et une unité structurelle (II) représentée par la formule générale (2) (où R4 représente un atome d'hydrogène ou un groupe méthyle ; R5 représente une liaison directe, CH2-, -CH2CH2- or -CO-; R6's'peuvent être identiques ou différents les uns des autres et représentent indépendamment un groupe alkylène ayant 1 à 20 atomes de carbone ; R7 représente un atome d'hydrogène ou un groupe alkyle ayant 1 à 20 atomes de carbone ; et m représente le nombre de moles de groupes oxyalkylène ajoutés et représente une valeur numérique de 1 à 100).
PCT/JP2019/008069 2019-03-01 2019-03-01 Agent conférant une capacité de prévention de l'encrassement et membrane de traitement de l'eau fabriquée à l'aide de celui-ci WO2020178892A1 (fr)

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US17/435,289 US11919986B2 (en) 2019-03-01 2019-03-01 Fouling prevention ability-imparting agent and water treatment membrane manufactured using same
PCT/JP2019/008069 WO2020178892A1 (fr) 2019-03-01 2019-03-01 Agent conférant une capacité de prévention de l'encrassement et membrane de traitement de l'eau fabriquée à l'aide de celui-ci
CN201980093283.XA CN113490540B (zh) 2019-03-01 2019-03-01 结垢抑制能力赋予剂和使用了该结垢抑制能力赋予剂的水处理膜
JP2021503248A JP7256505B2 (ja) 2019-03-01 2019-03-01 ファウリング抑制能付与剤およびそれを用いてなる水処理膜

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CN113490540B (zh) 2024-05-31

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